For many years, petroleum products have been recovered from subterranean reservoirs through the use of drilled wells and production equipment. The growing need for oil coupled with the decline in primary production of oil has required the need for more novel and efficient methods of recovering residual oil.
Many flow back aids have been developed and discussed in the prior art to help recover injected fluids after drilling or hydraulic fracturing. General information on hydraulic fracturing may be found in articles by Montgomery, J. Pet. Tech. (2010) 26-32 and by Beckwith, J. Pet. Tech. (2010) 34-41. Flow back aids benefit production by reducing damage due to phase trapping, enhance mobilization of the oil and gas, help to increase the regained permeability and improve the oil/gas recovery.
Flowback aid formulations generally include one or more anionic, nonionic or amphoteric surfactants, along with solvents and co-surfactants that are in the solution or microemulsion form. The various flowback aids are discussed by Howard et al. in SPE paper 122307. Also Panga, et al. discusses the effects of wettability alteration by flowback aids in SPE 100182.
Pursley et al., U.S. Pat. No. 7,380,606 discloses a microemulsion well treatment formed by combining a solvent-surfactant blend with a carrier fluid. In the preferred embodiments, the solvent-surfactant blend includes a surfactant and a solvent selected from the group consisting of terpenes and alkyl or aryl esters of short chain alcohols. Surfactants include ethoxylated castor oil, polyoxyethylene sorbitan monopalmitate and polyethylene glycol. Additionally, isopropyl alcohol and triethylene glycol are used in some cases. Penny and Pursley in SPE 86556 and SPE 107844 give field and laboratory data supporting the effectiveness of microemulsions in low perm shales, coalbed methane and tight sandstone reservoirs. The use and optimization of microemulsion based flowback aids for shale and tight gas reservoirs has also been described by Rickman et al. in SPE 131107.
More recently, microemulsion flowback aids have been published by Berger et al. in U.S. Pat. No. 7,998,911 using a blend of water soluble ester of a low molecular weight alcohol and a low molecular weight organic acid, an oil soluble ester of a low molecular weight alcohol and a high molecular weight fatty acid, one or more water soluble or dispersible nonionic surfactant(s) derived from vegetable or animal sources, one or more anionic or amphoteric surfactant(s) derived from animal or vegetable based sources, and, water.
Another example of a microemulsion system for gas well treatment has been disclosed by Kakdjian et al. in U.S. Pat. No. 8,220,546 which comprises a solvent subsystem, a co-solvent subsystem and a surfactant subsystem comprising at least one monoalkyl branched propoxy sulfate anionic surfactant useful in drilling, producing, remediation, and hydraulic fracturing application to reduce water blocking in reservoir and producing oil and gas wells.
U.S. Pat. No. 3,002,923 teaches a water-in-oil emulsion system that comprises saturated salt water, fuel oil, oil-soluble glucamide surfactants and a free-flowing solids (e,g. bentonite and barium sulfate) serving as drilling muds to remove drill cuttings from bore hole during the construction of a well. The reference teaches a content of the emulsion in glucamides from 1-4 wt.-%, a solvent content of 2-12 wt.-% and a solids content of up to 60 wt.-%.
X. D. Yang et al., Colloid Journal, 2007, Vol. 69, p. 252-258 and Journal of Colloid and Interface Science 320 (2008), 283-289 teach emulsions comprising water, solvents and glucamide surfactants that are Winsor type I, II or III emulsions.
J. Baran et al., Environmental Science and Technology 1996, 30, 2143-2147 teaches that a water/chlorocarbon microemulsion comprising glucamides shows a Winsor type I, II or III behaviour.
Although a number of microemulsion systems for use in oil and gas industry are known in the prior art, there is a continued need for more effective microemulsion systems. Especially there is still a need of flowback aids which are efficient in low concentrations, resistant to high salinities in the reservoirs, stable at higher temperature range which can occur during drilling or stimulation treatments. Such chemical aids are suitable not only for gas well application but also for use in liquid hydrocarbon reservoir applications, and provide very low interfacial tensions that supports maximum reduction of liquid phase trapping and faster fluid return and clean up.
In addition, other undesirable downhole products must be managed by well service fluids during the production of hydrocarbons. For example, scale, paraffins, fines, sulfur, heavy oil tar by-products and water blocks commonly accumulate in and around the formation, well casing, production tubing and recovery equipment. Alternatively, it may be necessary to remove injected fluids from the near wellbore area, such as drilling fluids, cement filtrate, kill fluids, polymers and water blocks. To maintain an efficient recovery of hydrocarbon products, it is frequently necessary to clean or remove these accumulations and deposits. The removal of unwanted deposits from the wellbore and production equipment is generally referred to as “remediation.” Microemulsion flowback aids of this invention may be used in remediation applications. In well remediation applications, the selected well treatment microemulsion is preferably injected directly into the wellbore through the production tubing or through the use of coiled tubing or similar delivery mechanisms. Once downhole, the well treatment microemulsion remedies drilling damage, fracturing fluid damage, water blocks and removes fines, asphaltenes and paraffins from the formation and wellbore.
The primary object of the invention is to provide a flowback aid formulation with strong interfacial tension reduction, surface wettability modification and high performance in fluid regain testing and better non-emulsification effect, thus having superior performance to the formulations disclosed in the prior art. Another object of the present invention is to provide a flowback formulation suitable for application under extreme conditions, such as very high salinities as well as high temperatures that are sometimes encountered during drilling and fracturing of oil and gas reservoirs.
It has now been found that a microemulsion from water, at least two solvents and a glucamide surfactant is a particularly effective well treatment fluid when the microemulsion is a Winsor type IV oil-in-water microemulsion.
In a first aspect, the present invention provides a well treatment microemulsion, comprising
water,
2-15 wt.-% of at least one organic solvent with flash point above 37.8° C. (100° F.) and pour point of 10° C. or lower,
1-6 wt.-% of at least one co-solvent that includes at least one alcohol, and
12-30 wt.-% of at least one N-Alkyl-N-acylglucamine surfactant,
which is a Winsor type IV emulsion.
In another aspect, this invention relates to a process for recovering fluids during fracturing operations, the process comprising injecting a microemulsion according to this invention into the fractured formation.
In another aspect, this invention relates to a process for stimulating an oil or gas well, comprising injection of water and the microemulsion according to the invention.
In another aspect, this invention relates to the use of the microemulsion according to the invention as flowback aid during fracturing operations.
In another aspect, this invention relates to the use of the microemulsion according to the invention in stimulating an oil or gas well by water injection.
In this specification, the expression “microemulsion system” with respect to this invention shall mean a system of water, oil and an amphiphile which is a single optically isotropic and thermodynamically stable liquid solution and is Winsor type IV. In some respects, microemulsions can be considered as small-scale versions of emulsions, i.e., droplet type dispersions either of oil-in-water (o/w) or of water-in-oil (w/o), with a size range in the order of 5-50 nm in droplet radius, suitable for increasing gas and/or oil production and water recovery. Microemulsions, are thermodynamically stable compositions and are formed spontaneously or with gentle agitation once the correct composition is reached. They have potentially infinite lifetimes depending on storage conditions. Other distinctions include droplet size and the color of the system. Conventional emulsions generally have spherical droplets with diameters large enough to scatter white light and are therefore opaque in appearance, whereas microemulsions have droplet sizes of 50 nm or less and are transparent or have slightly bluish tinge. The expression “surfactant subsystem” shall mean one or more surfactants suitable for use in the microemulsion. The expression “solvent subsystem” shall mean one or more solvents suitable for use in the microemulsion. The expression “co-solvent subsystem” shall mean one or more co-solvents suitable for use in the microemulsion.
According to Winsor, there are four types of microemulsion phases that exist in equilibria; these phases are referred to as Winsor type I to IV phases:    1. Winsor I: With two phases, the lower (o/w) microemulsion phases in equilibrium with the upper excess oil.    2. Winsor II: With two phases, the upper microemulsion phase (w/o) microemulsion phases in equilibrium with lower excess water.    3. Winsor III: with three phases, middle microemulsion phase (o/w plus w/o, called bicontinous) in equilibrium with upper excess oil and lower excess water.    4. Winsor IV: In single optically pure phase, with oil, water and surfactant homogenously mixed.
The instant invention relates to type IV microemulsions. These differ from type I, II or III microemulsions in that type IV microemulsions contain water, a non-aqueous fluid and a surfactant in a single phase. In type IV microemulsions no phase separation occurs over an extended time. The composition of the instant invention therefore is a microemulsion formed from water, at least one solvent, at least one co-solvent and a glucamide containing surfactant that is present in a single phase. For properties of microemulsions, reference in made to SPE paper 173729.
The inventors have found that new thermodynamically stable, microemulsion systems of Winsor type IV including a surfactant subsystem, a solvent subsystem and water, where the systems are substantially optically isotropic, are capable of increasing gas and/or oil production and water recovery. The new microemulsion systems and uses thereof afford faster fluid return and clean up and enhanced production in fractured tight gas and oil subterranean formations. The inventors have found that by including N-Alkyl-N-acylglucamine sugar surfactants or the cyclic N-Alkyl-N-acylglucamine derivatives into the surfactant subsystem of a microemulsion system the performance characteristics of the microemulsion system could be enhanced. Especially the interfacial tension reduction, the resistance against high salinity and stability at elevated temperatures could be improved compared to prior art microemulsion systems.
In certain embodiments, the new thermodynamically stable, microemulsion systems include a nonionic surfactant or a plurality of nonionic surfactants, an anionic surfactant or a plurality of anionic surfactants, a co-solvent subsystem, and a solvent system including heavy aromatic naphtha, paraffinic base oils or methylated fatty acids and water, where nonionic surfactant or surfactants includes glucamides or their cyclic derivatives.
The flowback aid composition of the present invention preferably includes the components a) to e) as follows:
a) a surfactant including at least one N-Alkyl-N-acylglucamine according to formula (I)
wherein    Ra is a linear or branched, saturated or unsaturated C5-C21-hydrocarbon residue, preferably a C7-C13-hydrocarbon residue, and    Rb is a C1-C4 alkyl residue, preferably methyl.
In another preferred embodiment, the N-Alkyl-N-acylglucamines (I) comprise at least 50 wt.-% of the total amount of N-Alkyl-N-acylglucamines (I) compounds with C7-C9-alkyl residue and up to 50 wt-% of the total amount of N-Alkyl-N-acylglucamines (I) compound with C11-C13-alkyl residue.
In another preferred embodiment, the surfactant includes at least one cyclic N-Alkyl-N-acylglucamine of the formulae (II), (III) and (IV)
wherein    Ra is a linear or branched, saturated or unsaturated C5-C21-alkyl residue, preferably a C7-C13-alkyl residue, and    Rb is a C1-C4-alkyl residue, preferably methyl.
In another preferred embodiment, the cyclic N-Alkyl-N-acylglucamines (II; III; IV) comprise at least 50 wt.-% of the total amount of cyclic N-Alkyl-N-acylglucamines (II; III; IV) compounds with C7-C9-alkyl residue and up to 50 wt.-% of the total amount of cyclic N-Alkyl-N-acylglucamines (II; III; IV) compound with C11-C13-alkyl residue.
The surfactant may additionally include non-ionic co-surfactants, such as linear or nonlinear ethoxylated alcohols, alkyl polyglycosides, castor oil ethoxylates, sorbitan ester derivatives or ethylene oxide/propylene oxide block copolymers. The preferred co-surfactants have an HLB value between about 5 and about 15. The surfactant may further include at least one anionic or amphoteric surfactant, such as alkylethersulfates, carboxy ether sulfates, sodium alkyl sulfosuccinates, sodium di-alkyl sulfosuccinates, alkylamidopropyl betaines and alkyl amine oxides.
b) A first solvent including at least one organic solvent with flash point above 37.8° C. (100° F.) and pour point of 10° C. or lower. In one preferred embodiment, the organic solvent can include naphthalene depleted alkyl arenes or a mixture thereof. In other embodiments, the organic solvent includes a terpene or a mixture of terpenes. Other embodiments use mineral oils, preferably paraffinic base oils. In yet another embodiment the organic solvent includes alkyl esters of fatty esters, in particular rapeseed oil methylester can be employed. In another embodiment, the solvent is a butyl glycol ether preferably having 1-10 ethoxy groups.c) A co-solvent, including at least one alcohol. In a preferred embodiment, this alcohol being the co-solvent may be a monohydric alcohol with a C1-C20-alkyl residue or a diol with a C2-C20-alkylene residue. It is believed to serve as a coupling agent between the solvent and the surfactant, thereby stabilizing the microemulsion. The alcohol also lowers the freezing point of the well treatment microemulsion. Although propylene glycol is presently more preferred, alternative suitable alcohols include midrange primary, secondary and tertiary monohydric alcohols and diols with between 1 and 20 carbon atoms, more preferably 2 to 10 carbon atoms, such as isopropanol, t-butanol, n-butanol, n-pentanol, n-hexanol, n-octanol and pentane-diol.d) Optionally a mutual solvent selected from the group consisting of 2-ethyl-hexanol, ethylene glycol ether of 2 ethyl-hexanol, polyethylene glycol ethers of 2 ethyl-hexanol, butyl glycol ether and propylene glycols for better coupling between solvent and the surfactant and lowering the freezing point of the microemulsion system. Said glycol ethers will comprise preferably 1 to 10 alkylene oxy units, e.g. ethoxy or propoxy units.e) Water, whereas the water can be fresh water, produced water or brine.
The composition of the present invention is preferably prepared by combining the N-Alkyl-N-acylglucamine surfactant, optionally the co-surfactant, of the first solvent, the co-solvent, optionally the mutual solvent, with the remainder being water. The mutual solvent and other compounds including but not limited to polyglycolethers may be added to improve stability and performance when necessary.
The inventive composition comprises 12-30 wt.-%, preferably 14-25 wt.-% of at least one N-Alkyl-N-acylglucamine surfactant.
The inventive composition comprises 2-15 wt.-%, preferably 5-10 wt.-% of at least one organic solvent with flash point above 37.8° C. (100° F.) and pour point of 10° C. or lower.
The inventive composition comprises 1-6 wt.-%, preferably 3-5 wt.-% of at least one co-solvent including at least one alcohol.
If present, the inventive composition comprises up to 10 wt.-%, preferably 4-10 wt.-%, more preferably 3-5 wt.-% of at least one co-surfactant.
If present, the inventive composition comprises up to 10 wt.-%, preferably 4-10 wt.-%, more preferably 3-5 wt.-% of at least one mutual solvent.
The remainder of the composition may be water.
If no Winsor type IV emulsion is formed directly, this can be remedied by increasing surfactant concentration and/or changing or reducing solvent content within the limits given above.
The microemulsions of this invention are adapted to be added to water-based fracturing fluids for stimulation of oil and gas bearing formations in concentrations between about 0.1 gptg (gallons per thousand gallons) and about 10 gptg depending on reservoir conditions to obtain the desired flowback performance. At this concentration range, the microemulsion improves removal of water block or well service fluid block (speeds up the removal of water blocks) thereby improving hydrocarbon production. Most of the commercially available microemulsions for these applications have been formulated with only non-ionic surfactants having a cloud point for either the mother solution or the treating solution of only 150° F. or lower, whereas many anionic systems are not resistant to high salinities. Another problem related to the systems according to the state of the art is that the interfacial tension reduction is insufficient in order to provide for faster flowback.
The present invention also involves a process for the treatment of conventional and non-conventional oil and gas reservoirs using the microemulsions above including but are not limited to drilling and stimulation of subterranean reservoirs including but not restricted to shale oil or gas, tight oil or gas, or coal bed methane. In general conventional oil and gas are easier and cheaper to produce than unconventional oil and gas. For example it is easier to produce oil from high permeability reservoir (>10 mD) than low permeability one (<1 mD). A reference on conventional and unconventional reservoirs can be found in SPE paper 152596.
The composition of the present invention is used at 0.1 to 10 gallons per thousand gallons of injected well treatment fluid. In most common application 1 to 5 gallons per thousand gallons may be used. The injected fluid may be fresh water, produced water, KCl solution, NaCl solution, acid solution or the combination of two or more of these. In general any aqueous fluid used for fracturing may be employed. The microemulsion of this invention is added to the injected fluid into the formation to reduce surface and interfacial tension and/or increase wettability to water allowing enhanced fluid recovery during drilling or stimulation processes. The injection fluid may contain, in addition to the microemulsion, other ingredients known to those familiar with the art including but not restricted to corrosion inhibitors, acids, dispersants, gelling agents, lubricity agents, oxygen scavengers, scale inhibitors, biocides, friction reducers, crosslinker, surfactants, pH adjuster, iron control agents, sands or ceramic proppants and gel breakers.
Employing the microemulsion improves penetration into the reservoir, allows better drainage and flowback, improves load recovery, and reduces formation damage due to fluid trapping, in addition to providing a safer solution to existing flowback aids due to lower toxicity and higher biodegradability. Other applications of the microemulsion include reservoir wettability alteration, well cleanout and work-over.